Quaternary diaminobenzoquinones

ABSTRACT

2,5-diamino-1,4-benzoquinones are used in the production of hair dye compositions and can be prepared by condensing a corresponding 3-amino-4-methoxy phenol derivative on one of a corresponding hydroxy aniline or phenylenediamine derivative, a corresponding benzoquinone imine derivative or a corresponding nitroso derivative.

This is a division of Ser. No. 862,827, filed Dec. 21, 1977, now U.S.Pat. No. 4,204,059 which is a division of Ser. No. 762,272, filed Jan.25, 1977, now U.S. Pat. No. 4,084,052, which is a division of Ser. No.600,786, filed July 31, 1975, now U.S. Pat. No. 4,023,926, which is adivision of Ser. No. 370,737, filed June 18, 1973, now U.S. Pat. No.3,919,265.

The present invention relates to new 2,5-diamino-1, 4-benzoquinones ofthe formula: ##STR1## wherein R₁, R₂, R₃ and R₄, each independentlyrepresent a member selected from the group consisting of hydrogen,halogen, lower alkyl having 1-4 carbon atoms and lower alkoxy having 1-4carbon atoms; R₅ represents a member selected from the group consistingof hydrogen, lower alkyl containing 1-4 carbon atoms and lower alkylhaving 1-4 carbon atoms and substituted with a member selected from thegroup consisting of hydroxyl and ##STR2## wherein n is 2-6 andpreferably 2, and R₈ and R₉ each independently are selected from thegroup consisting of hydrogen, alkyl having 1-4 carbon atoms and alkylhaving 1-4 carbon atoms and substituted by a member selected from thegroup consisting of hydroxy and acylamino wherein the acyl is aliphatichaving 2-5 carbon atoms or R₈ and R₉ together with the nitrogen atom towhich they are attached form a six-membered heterocycle capable ofincluding an oxygen heteroatom such as piperidinyl or morpholinyl; and Zrepresents a member selected from the group consisting of hydroxyl,##STR3## wherein R₆ and R₇ each independently represent a memberselected from the group consisting of hydrogen, lower alkyl having 1-4carbon atoms and lower alkyl having 1-4 carbon atoms and substituted bya member selected from the group consisting of hydroxyl, carbamyl,acylamino wherein acyl has the meaning given above, mesylamino andbenzoylamino, and ##STR4## wherein n represents 2-6, preferably 2, andR₁₀ and R₁₁ each independently represent a member selected from thegroup consisting of lower alkyl having 1-4 carbon atoms, lower alkylhaving 1-4 carbon atoms and substituted by a member selected from thegroup consisting of hydroxyl and acylamino wherein acyl has the meaninggiven above, and R₁₀ and R₁₁ together with the nitrogen atom to whichthey are attached form a six-membered heterocycle capable of includingan oxygen heteroatom, such as piperidinyl or morpholinyl.

The present invention also relates to the salts of the compounds offormula I with mineral or organic acids such as the hydrochloride,hydrobromide, and sulfate thereof and to the quaternary ammonium saltsof those compounds which have a tertiary amino group.

The compounds of the present invention can be prepared by condensing a3-amino-4-methoxy phenol of the formula ##STR5## wherein R₅ has themeaning given above or on a salt of said compound formed with a mineralor organic acid, on a member selected from the group consisting of

(a) a compound of the formula ##STR6## wherein Z, R₁, R₂, R₃ and R₄ havethe meanings given above, or a salt of said compound, the molar ratio ofcompounds III/II being preferably between 0.75-1.75, the condensationbeing carried out at a temperature between 5°-40° C. at atmosphericpressure;

(B) a benzoquinone-monoimine or diimine of the formula: ##STR7## whereinZ' represents a member selected from the group consisting of oxygen orimine and R₁, R₂, R₃ and R₄ have the meanings given above with theproviso that at least two of R₁, R₂, R₃ and R₄ are other than hydrogen.The condensation is carried out, preferably, at a temperature between5°-40° C. at atmospheric pressure. The molar ratio of compounds IV/II ispreferably equal to 1; and

(c) a nitroso derivative of the formula: ##STR8## or a salt thereof,wherein Z, R₁, R₂, R₃ and R₄ have the meanings given above, thecondensation being carried out, preferably, at a temperature between15°-80° C. at atmospheric pressure, the molar ratio of compounds V/IIbeing between 1-1.5.

The condensation of compounds III or IV on compound II is carried out inan aqueous, hydroacetonic or hydroalcoholic medium at a pH made alkalineby the addition thereto of, for example, ammonia, and in the presence ofa large excess of H₂ O₂ (10-75% H₂ O₂ --20 volumes), compounds III, IVand II generally being used in equimolar amounts.

The condensation of compound V on compound II is carried out in anaqueous, hydroalcoholic (the proportion of alcohol varying between0-100%) or hydroacetonic (the proportion of acetone being between 0-50%)medium, or even in absolute ethyl alcohol, especially when compound I isisolated in salt form. Compounds V and II are preferably employed inequimolar amounts and the pH of the reaction medium can either be madealkaline by the addition thereto of ammonia, or made slightly acid bythe addition thereto of acetic acid. It will be noted that the reactionmedium itself is acidic when the compound used in a hydrochloride,hydrobromide or sulfate of compound V and thus the addition of acid tothe reaction medium in this case would generally be superfluous.

The condensation of compound V on compound II is generally carried outin the presence of H₂ O₂. However, the presence of H₂ O₂ is notnecessary in certain instances, particularly when the reaction iscarried out in absolute ethyl alcohol and when the compound V utilizedis in the form of a salt thereof. The amount of H₂ O₂ (20 volumes)employed can vary between 0-75 percent by weight of the reactionmixture.

When compound I carries a quaternizable tertiary amine function thequaternary amine of this compound can be prepared by reacting it with analkylating agent such as methyl or ethyl sulfate, methyl or ethyl iodideor bromide, or benzylchloride. The quaternization reaction can becarried out at ambient temperature in an appropriate solvent such asdioxane or a mixture of dioxane and ethanol.

The compounds of the present invention are usefully employed as dyeswhich exhibit good affinity for keratinic fibers, particularly humanhair.

It is known, for instance, that many dyes for coloring hair often impartto the same a reddish glint or hue which is not always desirable. Thepresent invention however provides a solution to this problem. Thediamino benzoquinones of the present invention impart to keratinicfibers a wide range of green glints which diminish or suppress the redglints or highlights of conventional colorations, particularly red hair.

Diaminobenzoquinones, generally, are already known. Thus, U.S. Pat. No.2,267,741 and French Pat. No. 847,026 describe diamino benzo 1,4-quinoneof the formula ##STR9## wherein X and Y can represent hydrogen; and R₁and R₂, different from one another, can be hydrogen, alkyl or aryl.These compounds are dyes which dye wool yellow, brown or red-brown andare not suitable for the present purposes.

German patent No. 300,706 describes some monoaryl and diarylaminoquinones which dye wool yellow or brown. These compounds also arenot suitable for the present purposes.

French patent No. 1,554,722 describes aminoquinones that are used asantioxidants for a lubricant, rubber and plastic material.

The present invention also relates to a new industrial productcomprising a dye composition for keratinic fibers, particularly humanhair, comprising a solution of at least one compound of formula I or asalt thereof or a quaternary ammonium derivative thereof.

The compositions of the present invention are aqueous solutions whichcan also include one or more low molecular weight alcohols, such asethanol or isopropanol, or one or more glycols, such as butylglycol orpropylene glycol, so as to facilitate the dissolution of the dye in thewater. The amount of alcohol can vary, for instance, between about 5-70weight percent of the composition while the amount of glycol can varygenerally between about 2-5 weight percent of said composition.

The concentration of the compounds of formula I, or their salts, in thedye compositions of this invention can range between about 0.005-0.5,and preferably between about 0.005-0.25, percent by weight of saidcomposition.

The pH of the compositions of this invention can vary between about4-11, the compounds of formula I and their salts, exhibiting strongdyeing power in this extensive pH range. The pH of the compositions canbe adjusted to the desired value by the addition thereto of pH adjustingagents conventionally employed in cosmetic compositions such as, forinstance, an acid including for example orthophosphoric acid, lacticacid or acetic acid, or a base such as ammonia or triethanolamine.

The compositions of the present invention can include as the dyecomponent only the compounds of formula I, or salts thereof, in whichcase they provide a wide range of very luminous green solutions rich inmetallic glints, ranging from silvery almond green to very dark green,passing through light bronze, ash blonds and linden colors with goldenglints.

The compositions of the present invention can, however, include otherdirect dyes, for example, azo dyes, anthraquinone dyes, nitro dyes ofthe benzene series, indophenols, indoanilines, indamines or oxazines.The present composition can also include oxidation dyes such as di- ortri-amino phenols or amino diphenols.

Further, the compositions of the present invention can also includeadjuvants conventionally employed in cosmetic compositions such aswetting agents, emollients or perfumes. The compositions can also bepackaged under pressure in aerosol containers with a conventionalliquefied aerosol propellant such as a fluoronated hydrocarbon includingdichlorodifluoromethane, trichloromonofluoromethane and mixturesthereof, and other halogeneted hydrocarbons.

The compositions of the present invention, in one embodiment, can beemployed to provide durable hair colorations. In this embodiment thecompositions are applied to the hair for a period ranging from about10-30 minutes, the thus-treated hair thereafter being rinsed, washed anddried.

The present compositions can also be employed as a hair rinse lotion foruse in imparting to the hair a slight coloration. In this embodiment thecompositions are applied to washed hair, which application is notfollowed by any rinsing operation.

Further, the compositions of the present invention can be used as a hairsetting lotion to impart a slight coloration to the hair and to improvethe holding power of the set. In this embodiment, the compositionscomprise a hydroalcoholic solution of the dye component in combinationwith at least one cosmetic film-forming resin. The hair setting lotionis applied to previously washed and rinsed wet hair, followed by rollingthe hair up on curlers and drying the hair.

Representative cosmetic film-forming resins usefully employed in thehair setting lotions of this invention include polyvinylpyrrolidone,having a molecular weight between 40,000 and 400,000; copolymers ofvinylpyrrolidone and vinyl acetate (70-30:30-70%); copolymers of vinylacetate and an unsaturated carboxylic acid such as crotonic acid (90:10)having a molecular weight of about 20,000-50,000; copolymers resultingfrom the copolymerization of vinyl acetate (75-85%), crotonic acid(5-18%) and an acrylic or methacrylic ester (5-15%), copolymersresulting from the copolymerization of vinyl acetate and an alkyl vinylether, copolymers resulting from the copolymerization of vinyl acetate(63-88%), crotonic acid (5-15%) and a vinyl ester (5-25%) of a longcarbon chain acid (10-22 carbon atoms) or an allyl or methallyl ester ofa long carbon chain acid (10-22 carbon atoms), copolymers resulting fromthe copolymerization of 65-80% ester of an unsaturated alcohol (2-12carbon atoms) and a short carbon chain acid (2-5 carbon atoms) or a7-12% unsaturated short chain acid (4-20 carbon atoms) and 10-20% atleast one ester of a saturated short chain alcohol (8-18 carbon atoms)and an unsaturated acid (4-20 carbon atoms) and copolymers resultingfrom the copolymerization of at least one unsaturated ester at at leastone unsaturated acid.

The preferred cosmetic film forming resins include polyvinylpyrrolidone,copolymers of crotonic acid and vinyl acetate, copolymers ofvinylpyrrolidone and vinyl acetate, copolymers of maleic anhydride andbutyl vinyl ether, terpolymers of methyl methacrylate-stearylmethacrylate-dimethyl methacrylate; and terpolymers of vinylacetate-allyl stearate and allyloxy-acetic acid.

The cosmetic film forming resin is generally present in amounts of about1-3 percent by weight of the total composition.

The alcohols conveniently employed to produce the hair setting lotionsaccording to the present invention are low molecular weight alcohols,preferably, ethanol or isopropanol, which are present in amountsgenerally of about 20-70 percent by weight of said composition.

The following examples are given to illustrate the invention. In theexamples an ethyl alcohol at 96° corresponds to 950.189 g/kg of alcohol.

EXAMPLE 1

Preparation of 2-amino-5-(2'-methoxy-4'-amino anilino)-1,4-benzoquinoneof the formula: ##STR10## 0.02 mole (2.78 g) of 3-amino-4-methoxy phenolis dissolved in 200 cc of water to which has been added 20 cc of ammonia(22° Be') and 50 cc of H₂ O₂ (20 volumes). As soon as this solution hasbeen prepared, there is added, with agitation, a solution of 0.02 (4.27g) of methoxyparaphenylenediamine sulfate in 200 cc of water. After 4hours of agitation, the reaction mixture is filtered and the resulting2-amino-5-(2'-methoxy-4'-amino anilino)-1,4-benzoquinone is washed withwater. The raw product is then recrystallized in a mixture of dimethylformamide and water and dried under a vacuum with a boiling water bathfor 8 hours. The product exhibits a melting point of 267° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.13 H.sub.13 N.sub.3 O.sub.3                                                            Found                                                ______________________________________                                        C%        60.22          59.68      59.82                                     H%        5.05           5.11       5.08                                      N%        16.21          16.33      16.12                                     ______________________________________                                    

EXAMPLE 2

Preparation of 2-amino-5-(4'-dimethylamino anilino)-1,4-benzoquinone ofthe formula: ##STR11## 0.1 mole (13.9 g) of 3-amino-4-methoxy phenol isdissolved in 250 cc of water to which has been added 50 cc of ammonia(22° Be'). To this solution there are initially added 500 cc of H₂ O₂(20 volumes) and then, immediately thereafter, and with agitation, 0.1mol (20.9 g) of N,N-dimethylparaphenylene diamine dihydrochloride in 250cc of water. The reaction mixture is left to stand for 8 hours atambient temperature, at which time it is filtered to recover said2-amino-5-(4'-dimethylamino anilino)-1,4-benzoquinone. This raw product,after being washed with water, is recrystallized in dimethylformamideand dried under a vacuum with a boiling water bath for 5 hours. Theproduct exhibits a melting point of 300° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.14 H.sub.15 N.sub.3 O.sub.2                                                            Found                                                ______________________________________                                        C%        65.35          65.17      65.22                                     H%        5.88           6.01       5.79                                      N%        16.33          16.35      16.27                                     ______________________________________                                    

EXAMPLE 3

Preparation of 2-amino-5-(2'-methoxy-3',5'-dimethyl-4'-aminoanilino)-1,4-benzoquinone of the formula ##STR12##

0.01 mole (1.39 g) of 3-amino-4-methoxy phenol is dissolved in 30 cc ofwater to which has been added 8 cc of ammonia (22° Be'). To thissolution there are added 50 cc of H₂ O₂ (20 volumes) and immediatelythereafter, with good agitation, 0.01 mole (1.64 g) of2,6-dimethyl-3-methoxy-1,4-benzoquinone-diimine. After agitating theresulting mixture for about twenty minutes, the same is filtered torecover the above 2-amino-5-(2'-methoxy-3',5'-dimethyl-4'-aminoanilino)-1,4-benzoquinone which is then washed with water. Afterrecrystallizing the same in a mixture of dimethylformamide and water anddrying for five hours under a vacuum with a boiling water bath, theproduct exhibits a melting point of 214° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.15 H.sub.17 O.sub.3 N.sub.3                                                            Found                                                ______________________________________                                        C%        62.70          62.53      62.61                                     H%        5.96           5.96       6.14                                      N%        14.63          14.55      14.43                                     ______________________________________                                    

EXAMPLE 4

Preparation of 2-amino-5-(2'-methoxy-5'-methyl-4'-aminoanilino)-1,4-benzoquinone of the formula ##STR13##

0.01 mole (1.39 g) of 3-amino-4-methoxy phenol is dissolved in 20 cc ofwater to which has been added 10 cc of ammonia (22° Be') and 100 cc ofH₂ O₂ (20 volumes). As soon as this solution has been prepared there isadded, with good agitation, 0.01 mole (1.60 g) of2-methyl-5-methoxy-1,4-benzoquinone diimine. After a 30 minute reactionperiod, the reaction mixture is filtered to recover the expected2-amino-5-(2'-methoxy-5'-methyl-4'-amino anilino)-1,4-benzoquinone whichis then washed with water. The raw product is then recrystallized in amixture of dimethylformamide and water and dried for 6 hours under avacuum with a boiling water bath. The product exhibits a melting pointof 273° C.

Molecular mass calculated for C₁₄ H₁₅ O₃ N₃ =273

Molecular mass found by potentiometric dosage in acetic acid withperchloric acid=284

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.14 H.sub.15 O.sub.3 N.sub.3                                                            Found                                                ______________________________________                                        C%        61.53          61.21      61.36                                     H%        5.53           5.60       5.67                                      N%        15.38          15.55      15.27                                     ______________________________________                                    

EXAMPLE 5

Preparation of 2-amino-5-(4'-di-β-hydroxyethylaminoanilino)-1,4-benzoquinone of the formula ##STR14##

0.01 mole (1.39 g) of 3-amino-4-methoxy phenol is dissolved in 15 cc ofwater, 3 cc of acetic acid and 75 cc of H₂ O₂ (20 volumes). As soon asthis solution is prepared there is added, with good agitation, asolution of 0.01 mole (2.1 g) of 4-nitroso-N,N-di-β-hydroxyethyl anilinein 30 cc or a 50% aqueous ethanol solution. After agitating theresulting reaction mixture for two hours, the same is filtered torecover the expected 2-amino-5-(4'-di-β-hydroxyethylaminoanilino)-1,4-benzoquinone, which is then washed with water. The product,after recrystallization in a mixture of dimethylformamide and water anddrying for 10 hours under a vacuum with a boiling water bath, exhibits amelting point of 199° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.16 H.sub.19 N.sub.3 O.sub.4                                                            Found                                                ______________________________________                                        C%        60.55          60.62      60.62                                     H%        6.04           5.95       6.17                                      N%        13.24          13.47      13.20                                     ______________________________________                                    

EXAMPLE 6

Preparation of2-N-β-hydroxyethylamino-5-(2'-methoxy-3',5'-dimethyl-4'-aminoanilino)-1,4-benzoquinone of the formula ##STR15##

0.02 mole (3.66 g) of 3-N-β-hydroxyethylamino-4-methoxy phenol isdissolved in 30 cc of water, 16 cc of ammonia (22° Be') and 100 cc of H₂O₂ (20 volumes). As soon as this solution has been prepared there isadded thereto, with agitation, 0.02 mole (3.28 g) of2-methoxy-3,5-dimethyl-1,4-benzoquinonediimine. The resulting reactionmixture is agitated for 45 minutes at which time it is filtered torecover the2-N-β-hydroxyethylamino-5-(2'-methoxy-3',5'-dimethyl-4'-aminoanilino)-1,4-benzoquinone which is then washed with water. Afterrecrystallizing the same in a mixture of dimethylformamide and water anddrying under a vacuum with a boiling water bath for 8 hours, the productexhibited a melting point of 187° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.17 H.sub.21 O.sub.4 N.sub.3                                                            Found                                                ______________________________________                                        C%        61.63          61.27      61.32                                     H%        6.34           6.22       6.28                                      N%        12.68          12.57      12.82                                     ______________________________________                                    

EXAMPLE 7

Preparation of 2-amino-5-[4'-(N-ethyl,N-β-piperidinoethyl)aminoanilino]-1,4-benzoquinone of the formula: ##STR16##

To a solution of 0.04 mole (5.36 g) of 3-amino-4-methoxy phenol in 50 ccof water to which has been added 10 cc of ammonia (22° Be') and 200 ccof H₂ O₂ (20 volumes) there is added, with good agitation, 0.04 mole(13.3 g) of 4-nitroso-N-ethyl,N-β-piperidinoethyl anilinedihydrochloride in 50 cc of water. The resulting reaction mixture isagitated for a period of two hours at which time it is filtered torecover 2-amino-5-[4'-(N-ethyl,N-β-piperidinoethyl)aminoanilino]-1,4-benzoquinone which is then washed with boiling water. Thisproduct, after recrystallization in a mixture of dimethylformamide andwater and drying for 8 hours under vacuum with a boiling water bath,exhibits a melting point of 110° C.

Molecular mass calculated for C₂₁ H₂₈ N₄ O₂ =368

Molecular mass found by potentiometric dosage in acetic acid byperchloric acid=376

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.21 H.sub.28 N.sub.4 O.sub.2                                                            Found                                                ______________________________________                                        C%        68.45          68.45      68.40                                     H%        7.66           7.69       7.46                                      N%        15.21          14.98      15.17                                     ______________________________________                                    

EXAMPLE 8

Preparation of 2-amino-5-[4'-N-(ethyl,β-N-methylpiperidinium-ethyl)aminoanilino]-1,4-benzoquinone iodide of the formula: ##STR17##

0.0027 mole (1 g) of the compound of Example 7 is dissolved in 7 cc ofabsolute ethyl alcohol and 20 cc of dioxane. To this solution maintainedat 40° C. there are added, little by little, 3 cc of methyl iodide. Theresulting reaction mixture is left to stand for one hour at 40° C. atwhich time it is filtered to recover 1.3 g of the above quatenary saltwhich exhibits a melting point of 265° C.

    ______________________________________                                                  Calculated for                                                      Analysis  C.sub.22 H.sub.31 N.sub.4 O.sub.2 I                                                          Found                                                ______________________________________                                        C%        51.76          51.56      51.34                                     H%        6.08           6.16       6.14                                      N%        10.99          10.88      11.15                                      I%       24.90          25.00                                                ______________________________________                                    

EXAMPLE 9

Preparation of 2-N-β-hydroxyethylamino-5-(2'-methoxy-4'-aminoanilino)-1,4-benzoquinone of the formula: ##STR18##

To a solution of 0.01 mole (1.83 g) of 3-N-β-hydroxyethylamino-4-methoxyphenol in 25 cc of water to which has been added 10 cc of ammonia (22°Be') and 100 cc of H₂ O₂ (20 volumes) there is added, with goodagitation, 0.01 mole (2.10 g) of methoxyparaphenylene-diaminedihydrochloride in 25 cc of water. The resulting reaction mixture isagitated for two hours at which time it is filtered to recover2-N-β-hydroxyethylamino-5-(2'-methoxy-4'-amino anilino)-1,4-benzoquinonewhich is then washed with water. After recrystallizing the same in amixture of dimethyl formamide and water and drying under a vacuum with aboiling water bath for six hours, the product exhibited a melting pointof 215° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.15 H.sub.17 N.sub.3 O.sub.4                                                            Found                                                ______________________________________                                        C%        59.39          59.14      59.17                                     H%        5.65           5.73       5.78                                      N%        13.86          14.02      13.88                                     ______________________________________                                    

EXAMPLE 10

Preparation of2-N-β-hydroxyethylamino-5-[4'-(N-ethyl,N-β-piperidinoethyl)aminoanilino]-1,4-benzoquinone dihydrochloride of the formula: ##STR19##

There are heated for 45 minutes with a boiling water bath, 0.01 mole(3.33 g) of 4-nitroso-N,N-ethyl,β-piperidinoethyl anilidinedihydrochloride and 0.01 mole (1.83 g) of3-N-β-hydroxyethylamino-4-methyl phenol in 20 cc of absolute ethylalcohol. After filtering the boiling reaction mixture, the resultingfiltrate is cooled to 0° C. for a few hours at which time the cooledfiltrate is filtered to recover2-N-β-hydroxyethyl-amino-5-[4'-(N-ethyl,N-β-piperidinoethyl)aminoanilino]-1,4-benzoquinone dihydrochloride, which is washed with ethanoland then with acetone. The product is chromatographically pure and meltsat 226° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.23 H.sub.32 O.sub.3 N.sub.4 2HCl . H.sub.2 O                                                Found                                           ______________________________________                                        Cl%       14.11               13.97                                           ______________________________________                                    

EXAMPLE 11

Preparation of2-N-β-hydroxyethylamino-5-[4'-(di-β-hydroxyethylamino)anilino]-1,4-benzoquinoneof the formula: ##STR20##

0.01 mole (1.83 g) of 3-N-β-hydroxyethylamino-4-methoxy phenol isdissolved in 30 cc of acetone and 100 cc of H₂ O₂ (20 volumes). As soonas this solution has been prepared there is added, with good agitation,0.01 mole (2.46 g) of 4-nitroso-N-β-hydroxyethylaniline hydrochloride.The resulting reaction mixture is continued to be agitated for one hourat which time there are added thereto 10 cc of ammonia (22° Be') toprecipitate the2-N-β-hydroxyethylamino-5-[4'-di-β-hydroxyethylamino)anilino]-1,4-benzoquinone.This precipitate, after being filtered and washed with water, ischromatographically pure. After drying for 5 days under a vacuum atambient temperature, the product exhibited a melting point of 164° C.

Molecular mass calculated for C₁₈ H₂₃ O₅ N₃ =361

Molecular mass found by potentiometric dosage in acetic acid withperchloric acid=366

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.18 H.sub.23 N.sub.3 O.sub.5                                                            Found                                                ______________________________________                                        C%        59.82          59.28      59.17                                     H%        6.42           6.27       6.32                                      N%        11.62          11.49      11.56                                     ______________________________________                                    

EXAMPLE 12

Preparation of 2-amino-5-(3'-chloro-4'-hydroxyanilino)-1,4-benzoquinoneof the formula: ##STR21##

0.02 mole (2.78 g) of 3-amino-4-hydroxy phenol is dissolved in 200 cc ofwater to which have been added 20 cc of ammonia (22° Be'). To thissolution there are initially added 100 cc of H₂ O₂ (20 volumes) and thenimmediately thereafter, which good agitation, 0.02 mole (3.60 g) of2-chloro-4-amino phenol hydrochloride in 200 cc of water. The reactionmixture is left to stand for 5 hours at ambient temperature at whichtime it is filtered to recover the2-amino-5-(3'-chloro-4'-hydroxyanilino)-1,4-benzoquinone which is thenwashed with water, recrystallized in a mixture of dimethylformamide andwater and dried for 5 hours under a vacuum with a boiling water bath.The product is chromatographically pure.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.12 H.sub.9 O.sub.3 N.sub.2 Cl                                                          Found                                                ______________________________________                                        C%        54.44          54.07      54.12                                     H%        3.40           3.52       3.67                                      N%        10.58          10.36      10.30                                      Cl%      13.42          13.18      13.26                                     ______________________________________                                    

EXAMPLE 13

Preparation of 2-amino-5-(4'-hydroxy-2',3'-dimethylanilino)-1,4-benzoquinone of the formula: ##STR22##

0.01 mole (1.39 g) of 3-amino-4-methoxy phenol is dissolved in 100 cc ofwater to which have been added 50 cc of acetone and 10 cc of ammonia(22° Be'). To this solution there are added 100 cc of H₂ O₂ (20 volumes)and immediately thereafter, with good agitation, 0.01 mole (1.37 g) of2,3-dimethyl-4-amino phenol in suspension in 100 cc of water. Theresulting reaction mixture is agitated for three hours at which time itis filtered to recover the 2-amino-5-(4'-hydroxy-2',3'-dimethylanilino)-1,4-benzoquinone which is first washed with water and then withacetone. It is dried for 8 hours under a vacuum with a boiling waterbath and is chromatographically pure, melting at 320° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.14 H.sub.14 N.sub.2 O.sub.3                                                            Found                                                ______________________________________                                        C%        65.10          64.92      64.87                                     H%        5.46           5.52       5.57                                      N%        10.85          10.77      10.69                                     ______________________________________                                    

EXAMPLE 14

Preparation of 2-N-β-hydroxyethylamino-5-(2',5'-dimethyl-4'-hydroxyanilino)-1,4-benzoquinone of the formula: ##STR23##

0.02 mole (3.60 g) of 3-β-hydroxyethylamino-4-methoxy phenol isdissolved in 30 cc of acetone to which have been added 2 cc of ammonia(22° Be') and 150 cc of H₂ O₂ (20 volumes). As soon as this solution hasbeen prepared there is added, at ambient temperature and with goodagitation, 0.02 mole (3.02 g) of 2,5-dimethyl-4-nitrosophenol in 20 ccof acetone. The resulting reaction mixture is agitated for 5 hours at35° C. at which time it is filtered to recover said2-N-β-hydroxyethylamino-5-(2',5'-dimethyl-4'-hydroxyanilino)-1,4-benzoquinone which is washed with water and with acetone.After recrystallizing it in a mixture of dimethylformamide and water itexhibits a melting point of 249° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.16 H.sub.18 O.sub.4 N.sub.2                                                            Found                                                ______________________________________                                        C%        63.57          63.62      63.57                                     H%        5.96           6.01       6.01                                      N%        9.27           9.18       9.12                                      ______________________________________                                    

EXAMPLE 15

Preparation of2-N-β-diethylaminoethylamino-5-(4'-N,N-di-β-hydroxyethylaminoanilino)-1,4-benzoquinone of the formula: ##STR24##

0.01 mole (2.75 g) of 3-N-β-diethylaminoethylamino-4-methoxy phenolhydrochloride is dissolved in 50 cc of acetone, 100 cc of H₂ O₂ (20volumes) and 5 cc of ammonia (22° Be'). As soon as this solution hasbeen prepared there is added thereto, with agitation, 0.01 mole (2.46 g)of 4-nitroso-N,N-di-β-hydroxyethyl aniline hydrochloride. The resultingreaction mixture is agitated for one hour at which time there are addedthereto 5 cc of ammonia (22° Be'). The reaction mixture is then filteredto recover said2-N-β-diethylaminoethylamino-5-(4'-N,N-di-β-hydroxyethylaminoanilino)-1,4-benzoquinone which is then washed with water. The productis chromatographically pure and after drying for 5 days under a vacuumat ambient temperature it exhibits a melting point of 120° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.22 H.sub.32 N.sub.4 O.sub.4 . H.sub.2 O                                                Found                                                ______________________________________                                        C%       60.82           60.62     60.92                                      H%       7.83            7.65      7.70                                       N%       12.90           12.94     12.73                                      ______________________________________                                    

EXAMPLE 16

Preparation of 2-N-β-(methyl,diethylammonium)ethylamino-5-(4'-N,N-di-β-hydroxyethylaminoanilino)-1,4-benzoquinone iodide of the formula: ##STR25##

0.0023 mole (1 g) of the compound of Example 15 is dissolved in 7 cc ofabsolute ethanol and 20 cc of dioxane. To this solution, at ambienttemperature and with agitation, there are added, little by little, 3 ccof methyl iodide. The resulting reaction mixture is agitated for 8 hoursat which time it is filtered to recover 1.18 g of the above quaternarysalt which is then washed with a little dioxane and finally withsulfuric ether. It melts at 243° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.23 H.sub.35 N.sub.4 O.sub.4 I                                                          Found                                                ______________________________________                                        C%        49.46          49.12      49.19                                     H%        6.29           6.27       6.31                                      N%        10.03          10.00      9.80                                       I%       22.75          22.60                                                ______________________________________                                    

EXAMPLE 17

Preparation of 2-β-aminoethylamino-5-(2'-methoxy-3',5'-dimethyl-4'-aminoanilino)-1,4-benzoquinone of the formula: ##STR26##

0.01 mole (2.63 g) of 3-β-aminoethylamino-4-methoxy phenolmonohydrobromide is dissolved in 20 cc of water and 100 cc of H₂ O₂ (20volumes). As soon as this solution has been prepared and cooled in ice,there is added, with agitation, 0.01 mole (1.64 g) of2,6-dimethyl-3-methoxy-1,4-benzoquinonediimine. The resulting reactionmixture is agitated for a period of about 20 minutes at which time it isalkalinized to a pH of about 10 by the addition thereto of ammonia (22°Be'). The reaction mixture is then filtered to recover the2-β-aminoethylamino-5-(2'-methoxy-3',5'-dimethyl-4'-aminoanilino)-1,4-benzoquinone which is then washed with water. Afterrecrystallizing the same in a mixture of acetone and water and dryingfor several days under a vacuum at ambient temperature, the productexhibits a melting point of 96° C. and is chromatographically pure.

Molecular mass calculated for C₁₇ H₂₂ O₃ N₄ =330

Molecular mass found by potentiometric dosage in acetic acid withperchloric acid=348

EXAMPLE 18

Preparation of2-N-β-hydroxyethylamino-5-[2'-methyl-4'-(N-ethyl,N-β-mesylaminoethyl)aminoanilino]-1,4-benzoquinone of the formula: ##STR27##

0.01 mole (1.83 g) of 3-N-β-hydroxyethylamino-4-methoxy phenol isdissolved in 50 cc of a 50% hydroacetonic solution. To this solutionthere are added 25 cc of ammonia (22° Be') and 100 cc of H₂ O₂ (20volumes) and then, little by little, with agitation and whilemaintaining the temperature thereof at about 10° C., a solution of 0.01mole (4.36 g) of N-ethyl-N-β-mesylaminoethyl paratoluene diamine sulfatemonohydrate in 20 cc of water. The resulting reaction mixture isagitated for one hour at which time it is filtered to recover theprecipitate which has formed, which precipitate is the above product.The precipitate is washed with water, recrystallized twice in a mixtureof dimethylformamide and water and dried under a vacuum at 80° C. Theproduct exhibits a melting point of 158° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.20 H.sub.28 N.sub.4 O.sub.5 S                                                          Found                                                ______________________________________                                        C%        55.04          54.68      54.72                                     H%        6.41           6.39       6.32                                      N%        12.84          13.00      13.03                                      S%       7.34           7.30       7.27                                      ______________________________________                                    

EXAMPLE 19

Preparation of2-N-β-hydroxyethylamino-5-[(4'-N-ethyl,N-β-acetylaminoethyl)aminoanilino]-1,4-benzoquinone of the formula ##STR28##

To a solution of 0.05 mole (9.2 g) of 3-N-β-hydroxyethylamino-4-methoxyphenol in 200 cc of water to which has been added 5 cc of ammonia (22°Be') and 500 cc of H₂ O₂ (20 volumes), there is added, with goodagitation, a solution of 0.05 mole (11.7 g) of4-nitroso-N,ethyl,N-acetylamino-ethylaniline in 200 cc of acetone. Whenthe temperature of the reaction mixture reaches 35° C., the same is thencooled with ice. Agitation of the reaction mixture is continued for aperiod of two hours at which time the same is filtered to recover theprecipitate which has formed, said precipitate being theabove-identified product. The precipitate is washed and recrystallizedtwice with the aid of ethyl acetate. The resulting product exhibits amelting point of 164° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.20 H.sub.26 N.sub.4 O.sub.4                                                            Found                                                ______________________________________                                        C%        62.16          61.81      61.97                                     H%        6.78           6.57       6.84                                      N%        14.50          14.72      14.59                                     ______________________________________                                    

EXAMPLE 20

Preparation of 2-N-β-hydroxyethylamino-5-[2'-chloro-4'-N,N-diethylaminoanilino]-1,4-benzoquinone of the formula: ##STR29##

To a solution of 0.02 mole (3.66 g) of 3-N-β-hydroxyethylamino-4-methoxyphenol in 40 cc of water to which has been added 200 cc of H₂ O₂ (20volumes) and 2 cc of ammonia (22° Be'), there is added, with goodagitation, a solution of 0.02 mole (4.24 g) of3-chloro-4-nitroso-N,N-diethyl aniline in 100 cc of acetone. Theresulting reaction mixture is agitated for two hours at which time it isfiltered to recover the precipitate which has formed, said precipitatebeing the above product. The precipitate is then carefully washed withwarm water and after recrystallization in a mixture of diethylformamideand water and two recrystallizations in methylisobutyl ketone, theproduct exhibits a melting point of 158° C.

Molecular mass calculated for C₁₈ H₂₂ N₃ O₃ Cl=363.5

Molecular mass found by potentiometric dosage in acetic acid withperchloric acid=369

EXAMPLE 21

Preparation of 2-N-β-hydroxyethylamino-5-[4'-N(ethyl,β-piperidinoethyl)amino anilino]-1,4-benzoquinone of the formula:##STR30##

2.9 g of 2-N-β-hydroxyethylamino-5-[4'-N(ethyl,β-piperidinoethyl)aminoanilino]-1,4-benzoquinone are dissolved in 100 cc of water. The same isalkalinized to a pH of 8 by the addition thereto of ammonia (22° Be').The reaction mixture is then filtered to recover the precipitate whichhas formed, which precipitate is the above product, is then washed withwater and, after recrystallization in a mixture of dimethyl formamideand water and drying under a vacuum at 80° C., exhibits a melting pointof 174° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.23 H.sub.32 N.sub.4 O.sub.3                                                            Found                                                ______________________________________                                        C%        66.96          66.73      67.18                                     H%        7.82           7.79       7.72                                      N%        13.58          13.69      13.70                                     ______________________________________                                    

EXAMPLE 22

Preparation of 2-N-β-hydroxyethylamino-5[4'-[N-ethyl,β-(methylpiperidinium)ethyl]-amino anilino]-1,4-benzoquinone iodide of theformula: ##STR31##

0.0118 mole (5 g) of2-N-β-hydroxyethylamino-5-[4'-N(ethyl,β-piperidinoethyl)aminoanilino]-1,4-benzoquinone, prepared in accordance with the method setforth in Example 21, is dissolved in 35 cc of ethanol to which has beenadded 100 cc of dioxane. To this solution, maintained at a temperatureof 40° C., there are added, little by little, 20 cc of methyl iodide.The resulting reaction mixture is left to stand for 12 hours at ambienttemperature at which time it is filtered to recover the above quaternarysalt which is first washed with dioxane and then with ether. The productexhibits a melting point of 136° C.

    ______________________________________                                                    Calculated For                                                    Analysis    C.sub.24 H.sub.35 N.sub.4 O.sub.3 I                                                           Found                                             ______________________________________                                        I%          22.90           22.96                                             ______________________________________                                    

EXAMPLE 23

Preparation of2-N-β-hydroxyethylamino-5-[4'-(dimethylamino)anilino]-1,4-benzoquinoneof the formula: ##STR32##

There are introduced into 25 cc of absolute ethanol, (a) 0.016 mole (3g) of 4-nitroso dimethyl aniline hydrochloride, and (b) 0.011 mole (2 g)of 3-N-β-hydroxyethylamino-4-methoxy phenol. The resulting reactionmixture is heated to reflux, with agitation, for one hour at which timeit is filtered to recover the precipitate which has formed. Theprecipitate is then washed with ethanol and treated with 100 cc of anaqueous ammonia solution (11.5° Be') with agitation, for about 30minutes. The reaction mixture is then filtered to recover the2-N-β-hydroxyethylamino-5-[4'-(dimethylamino)anilino]-1,4-benzoquinonewhich after washing with water, recrystallization in a mixture ofdimethylformamide and water, and drying under a vacuum exhibits amelting point of 265° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.16 H.sub.19 N.sub.3 O.sub.3                                                            Found                                                ______________________________________                                        C%        63.77          63.65      63.77                                     H%        6.36           6.54       6.50                                      N%        13.95          13.95      13.84                                     ______________________________________                                    

EXAMPLE 24

Preparation of2-N-β-hydroxyethylamino-5-[4'-(amino)anilino]-1,4-benzoquinone of theformula ##STR33##

0.01 mole (1.85 g) of 3-N-β-hydroxyethylamino-4-methoxy phenol isdissolved in 25 cc of water, 25 cc of acetone, 10 cc of ammonia (22°Be') and 100 cc of H₂ O₂ (20 volumes). To this solution there isimmediately added 0.01 mole (1.81 g) of paraphenylene diaminedihydrochloride in 20 cc of water. The resulting reaction mixture isagitated for one hour at ambient temperature at which time it isfiltered to recover the 2-N-β-hydroxyethylamino-5-[4'-(amino)anilino]-1,4-benzoquinone, which is washed with water and dried under avacuum. After recrystallizing the same in a mixture of dimethylformamideand ether, the product exhibited a melting point of 248° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.14 H.sub.15 N.sub.3 O.sub.3                                                            Found                                                ______________________________________                                        C%        61.59          61.04      61.46                                     H%        5.53           5.67       5.56                                      N%        15.38          15.50      15.51                                     ______________________________________                                    

EXAMPLE 25

Preparation of 2-amino-5-[4'-(amino)anilino]-1,4-benzoquinone of theformula: ##STR34##

0.75 mole (10.5 g) of 3-amino-4-methoxy phenol is dissolved in 50 cc ofacetone to which have been added 50 cc of ammonia (22° Be') and 250 ccof H₂ O₂ (20 volumes). To this solution there is immediately added 0.05mole (9.0 g) of paraphenylene diamine dihydrochloride in solution in 100cc of water. The resulting reaction mixture is agitated for two hours atambient temperature at which time the reaction mixture is filtered torecover the precipitate which has formed. After recrystallizing theprecipitate in ethylacetate and washing the recrystallized productinitially with a little methyl cellosolve and then with a little ether,2-amino-5-[4'-(amino)anilino]-1,4-benzoquinone is obtained which ischromatographically pure and which melts with decomposition above 260°C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.12 H.sub.11 N.sub.3 O.sub.2                                                            Found                                                ______________________________________                                        C%        62.87          63.03      63.07                                     H%        4.84           5.12       5.07                                      N%        18.33          18.23      18.29                                     ______________________________________                                    

EXAMPLE 26

Preparation of2-N-β-hydroxyethylamino-5-[(2'-methoxy-5'-methyl-4'-amino)anilino]-1,4-benzoquinoneof the formula: ##STR35##

0.625 millimole (0.11 g) of 3-N-β-hydroxyethylamino-4-methoxy phenol isdissolved in 2 cc of water to which have been added 1 cc of ethanol, 0.5cc of ammonia (22° Be') and 3 cc of H₂ O₂ (20 volumes). As soon as thissolution has been prepared there is added thereto, with agitation, 0.62millimole (0.10 g) of 2-methyl-5-methoxy-1,4-benzoquinonediimine. Theresulting reaction mixture is agitated for 15 minutes at which time itis filtered to recover said2-N-β-hydroxyethylamino-5-[(2'-methoxy-5'-methyl-4'-amino)anilino]-1,4-benzoquinone,which is washed with water and then recrystallized in a mixture ofdimethylformamide and water. After drying the same under a vacuum itexhibited a melting point of 227° C.

    ______________________________________                                                    Calculated For                                                    Analysis    C.sub.16 H.sub.19 N.sub.3 O.sub.4                                                             Found                                             ______________________________________                                        C%          60.55           60.28                                             H%          6.04            6.14                                              N%          13.24           13.04                                             ______________________________________                                    

EXAMPLE 27

Preparation of2-N-β-hydroxyethylamino-5-[(2',5'-dimethyl-4'-amino)anilino]-1,4-benzoquinoneof the formula: ##STR36##

0.02 mole (3.66 g) of 3-N-β-hydroxyethylamino-4-methoxy phenol isdissolved in 50 cc of water to which have been added 20 cc of ammonia(22° Be') and 200 cc of H₂ O₂ (20 volumes). To this solution there isimmediately added, with agitation, 0.02 mole (4.18 g) of 2,5-dimethylparaphenylene diamine dihydrochloride in 50 cc of water. The resultingreaction mixture is agitated for 1.5 hours at ambient temperature, atwhich time it is filtered to recover the2-β-hydroxyethylamino-5-[(2',5'-dimethyl-4'-amino)anilino]-1,4-benzoquinonewhich is washed with water and recrystallized in acetone. After dryingunder a vacuum at 80° C. the product exhibited a melting point of 248°C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.16 H.sub.19 N.sub.3 O.sub.3                                                            Found                                                ______________________________________                                        C%        63.77          63.35      63.06                                     H%        6.36           6.42       6.15                                      N%        13.95          14.08      14.10                                     ______________________________________                                    

EXAMPLE 28

Preparation of 2-N-β-hydroxyethylamino-5-[4'-N-(ethyl,carbamylmethyl)amino anilino]-1,4-benzoquinone of the formula: ##STR37##

0.015 mole (2.7 g) of 3-N-β-hydroxyethylamino-4-methoxy phenol isdissolved in 25 cc of water to which have been added 10 cc of acetone,10 cc of ammonia (22° Be') and 10 ml of H₂ O₂ (30 volumes). To thissolution there is added, with agitation, 0.01 mole (1.93 g) ofN-(ethyl,carbamylmethyl) paraphenylene diamine in 20 cc of water. Theresulting reaction mixture is agitated for two hours at 30° C. at whichtime it is filtered to recover the2-N-β-hydroxyethylamino-5-[4'-N(ethyl,carbamylmethyl)aminoanilino]-1,4-benzoquinone which is washed with water and recrystallizedin a mixture of dimethylformamide and water. After drying under a vacuumat 80° C. the product exhibited a melting point of 252° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.18 H.sub.22 N.sub.4 O.sub.4                                                            Found                                                ______________________________________                                        C%        60.32          60.00      60.31                                     H%        6.19           6.03       6.25                                      N%        15.63          15.91      15.75                                     ______________________________________                                    

EXAMPLE 29

Preparation of 2-N-β-hydroxyethylamino-5-[4'-(N-ethyl,N-β-morpholinoethyl)amino anilino]-1,4-benzoquinone of the formula:##STR38##

0.015 mole (2.74 g) of 3-β-hydroxyethylamino-4-methoxy phenol isdissolved in 20 cc of acetone to which have been added 10 cc of ammonia(22° Be'). 50 cc of H₂ O₂ (20 volumes) are added thereto and immediatelythereafter, with agitation, 0.01 mole (3.36 g) of4-nitroso-N-ethyl,N-morpholinoethyl aniline dihydrochlorine in 25 cc ofwater is added. The resulting reaction mixture is agitated for two hoursat 30° C. at which time it is filtered to recover the precipitate whichhas formed, said precipitate being the above product. The precipitate isthen washed with water, recrystallized in a mixture of dimethylformamideand water, and dried under a vacuum. The resulting product exhibited amelting point of 195° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.22 H.sub.30 N.sub.4 O.sub.4                                                            Found                                                ______________________________________                                        C%        63.75          63.45      63.58                                     H%        7.30           7.23       7.37                                      N%        13.52          13.32      13.55                                     ______________________________________                                    

EXAMPLE 30

Preparation of2-N-β-hydroxyethylamino-5-[4'-N-(dibutylamino)anilino]-1,4-benzoquinoneof the formula: ##STR39##

Into 20 mm of ethanol (96°) there are introduced (a) 0.1 mole (1.83 g)of 3-N-β-hydroxyethylamino-4-methoxy phenol and (b) 0.01 mole (2.70 g)of 4-nitroso dibutylaniline hydrochloride. The resulting reaction isleft to stand, with agitation, for one hour at ambient temperature atwhich time it is filtered to recover the precipitate which has formed,which precipitate is the above product in the hydrochloride formthereof. This hydrochloride is dissolved in 30 cc of water and thenalkalinized to a pH of 8 by the addition thereto of ammonia (22° Be') toprecipitate the above 1,4-benzoquinone in the form of green crystals.After recrystallization in a mixture of dimethylformide and water anddrying under a vacuum, the product exhibited a melting point of 170° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.22 H.sub.31 N.sub.3 O.sub.3                                                            Found                                                ______________________________________                                        C%        68.54          68.76      68.72                                     H%        8.11           8.14       7.98                                      N%        10.90          10.97      10.96                                     ______________________________________                                    

EXAMPLE 31

Preparation of 2-N-β-hydroxyethylamino-5-[2'-methyl-4'-(N-ethyl,N-β-benzoylaminoethyl)amino anilino]-1,4-benzoquinone of the formula:##STR40##

Into 20 cc of ethanol (96°) there are introduced (a) 0.01 mole (1.83 g)of 3-N-β-hydroxyethylamino-4-methoxy phenol, and (b) 0.01 mole (3.47 g)of 3-methyl-4-nitroso-N-ethyl,N-β-benzoylamino ethyl anilinehydrochloride. The resulting reaction mixture is left to stand, withagitation, for one hour at 50° C. at which time it is filtered. Theresulting filtrate is diluted by the addition thereto of 30 cc of waterand alkalinized up to a pH of 8 by addition of ammonia (22° Be') andthen filtered to recover the above substituted 1,4-benzoquinone which isthen washed with water and recrystallized in a mixture ofdimethylformamide and water. After drying under a vacuum the productexhibited a melting point of 104° C.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.26 H.sub.30 O.sub.4 N.sub.4 . H.sub.2 O                                                 Found                                                ______________________________________                                        C%       64.98           64.85     64.77                                      H%       6.71            6.94      6.83                                       N%       11.66           11.47     11.52                                      ______________________________________                                    

EXAMPLE 32

Preparation of 2-N-β-hydroxyethylamino-5-[4'-morpholinoanilino]-1,4-benzoquinone of the formula: ##STR41##

0.015 mole (2.74 g) of 3-β-hydroxyethylamino-4-methoxy phenol isdissolved in 15 cc of acetone to which have been added 10 cc of ammonia(22° Be'). To this solution there are added 100 cc of H₂ O₂ (20 volumes)and immediately thereafter, with agitation, 0.01 mole (1.78 g) of4-N-[(amino)phenyl]morpholine in 25 cc of acetone. The resultingreaction mixture is agitated for 7 hours at ambient temperature at whichtime it is filtered to recover the precipitate which has formed, saidprecipitate being the above product. The precipitate is washed withwater, recrystallized in dimethylformamide and dried under a vacuum. Theproduct is chromatographically pure and melts above 260° C.

    ______________________________________                                                  Calculated For                                                      Analysis  C.sub.18 H.sub.21 N.sub.3 O.sub.4                                                            Found                                                ______________________________________                                        C%        62.96          62.40      62.78                                     H%        6.16           6.03       6.24                                      N%        12.24          12.00      12.17                                     ______________________________________                                    

EXAMPLES OF USE EXAMPLE 33

The following solution is prepared:

Dye of Example 5: 0.2 g

Butyl glycol: 5.0 g

Lauryl alcohol oxyethylenated with 10.5 moles of ethylene oxide: 5.0 g

Ammonia (22° Be') q.s.p.: pH 9

Water q.s.p.: 100.0 g

This solution is applied to bleached hair for a period of 20 minutes at35° C. After rinsing and shampooing there is imparted thereto a verysilvery almond green coloration.

EXAMPLE 34

The following solution is prepared:

Dye of Example 5: 0.025 g

Copolymer of 90% vinyl acetate- 10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water: 100.0 g

Triethanolamine, q.s.p.: pH 5

This hair setting lotion when applied to bleached hair imparts thereto apearly appearance with green glints.

EXAMPLE 35

The following solution is prepared:

Dye of Example 7: 0.25 g

Ethyl alcohol (96°): 40.0 g

Water, q.s.p.: 100.0 g

10% solution of lactic acid, q.s.p.: pH 4.5

This solution when applied to bleached hair for 15 minutes at 30° C.after rinsing and shampooing imparts thereto a very dark greencoloration with golden glints.

EXAMPLE 36

The following solution is prepared:

Dye of Example 8: 0.15 g

Ethyl alcohol (96°): 25.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 9

This solution when applied to 95% naturally white hair for 20 minutes atambient temperature, after rinsing and shampooing, imparts thereto asilvery gray-green coloration.

EXAMPLE 37

The following solution is prepared:

Dye of Example 5: 0.025 g

Ethyl alcohol (96°): 25.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be') q.s.p.: pH 10

This solution when applied to bleached hair for 20 minutes at 35° C.,after rinsing and shampooing imparts thereto a pearly pale greencoloration.

EXAMPLE 38

The following solution is prepared:

Dye of Example 8: 0.15 g

Ethyl alcohol (96°): 30.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be') q.s.p.: pH 8

This solution when applied to bleached hair for 20 minutes at 40° C.,after rinsing and shampooing imparts thereto a dark green colorationwith golden glints.

EXAMPLE 39

The following solution is prepared:

Dye of Example 10: 0.1 g

Butylglycol: 5.0 g

Lauryl alcohol oxyethylenated with 10.5 moles of ethylene oxide: 5.0 g

Ammonia (22° Be') q.s.p.: pH 7.5

Water, q.s.p.: 100.0 g

This solution when applied to bleached hair for 20 minutes at ambienttemperature, after rinsing and shampooing imparts thereto a silvery palegreen coloration.

EXAMPLE 40

The following solution is prepared:

Dye of Example 16: 0.25 g

Butylglycol: 5.0 g

Lauryl alcohol oxyethylenated with 10.5 moles of ethylene oxide: 5.0 g

Ammonia (22° Be'), q.s.p.: pH 9

Water, q.s.p.: 100.0 g

This solution when applied to 95% naturally white hair for 20 minutes at30° C., after rinsing and shampooing imparts thereto a very silvery darkgreen coloration.

EXAMPLE 41

The following solution is prepared:

Dye of Example 7: 0.2 g

Copolymer of 90% vinyl acetate- 10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Triethanolamine, q.s.p.: pH 7

This hair setting lotion when applied to bleached hair imparts thereto apearly almond green coloration.

EXAMPLE 42

The following solution is prepared:

Dye of Example 7: 0.05 g

Ethyl alcohol (96°): 40.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 8

This solution when applied to bleached hair for 20 minutes at 30° C.,after rinsing and shampooing imparted thereto a light green colorationwith golden glints.

EXAMPLE 43

The following solution is prepared:

Dye of Example 8: 0.025 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 9.5

This solution when applied to bleached hair for 20 minutes at ambienttemperature, after rinsing and drying imparted thereto a pearly almondgreen coloration.

EXAMPLE 44

The following solution is prepared:

Dye of Example 7: 0.1 g

Ethyl alcohol (96°): 30.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 10.5

This solution when applied to 90% naturally white hair for 20 minutes at40° C., after rinsing and shampooing imparted thereto a metallic greencoloration.

EXAMPLE 45

The following solution is prepared:

Dye of Example 11: 0.15 g

Ethyl alcohol (96°): 20.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 7

This solution when applied to bleached hair for 20 minutes at 30° C.,after rinsing and shampooing imparted thereto a pearly almond greencoloration.

EXAMPLE 46

The following solution is prepared:

Dye of Example 5: 0.1 g

Copolymer of 90% vinyl acetate- 10% crotonic acid (MW=45,000-50,000):1.0 g

Ethyl alcohol (96°): 36.0 g

Water, q.s.p.: 100.0 g

Triethanolamine, q.s.p.: pH 8

This hair setting lotion when applied to bleached hair imparts thereto avery luminous silvery pale green coloration.

EXAMPLE 47

The following solution is prepared:

Dye of Example 9: 0.1 g

Copolymer of 90% vinyl acetate- 10% crotonic acid (MW=45,000-50,000):1.0 g

Ethyl alcohol (96°): 36.0 g

Water, q.s.p.: 100.0 g

Triethanolamine, q.s.p.: pH 7

This hair setting lotion when applied to bleached hair imparts thereto alight bronze coloration.

EXAMPLE 48

The following solution is prepared:

Dye of Example 9: 0.01 g

Ethyl alcohol (96°): 20.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be') q.s.p.: pH 9

This solution when applied to bleached hair for 20 minutes at 40° C.,after rinsing and shampooing imparts thereto a linden coloration.

EXAMPLE 49

The following solution is prepared:

Dye of Example 6: 0.1 g

Copolymer of 90% vinyl acetate- 10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 6

This hair setting lotion when applied to bleached hair imparts thereto asilvery almond green coloration.

EXAMPLE 50

The following solution is prepared:

Dye of Example 14: 0.15 g

Copolymer of 90% vinyl acetate- 10% crotonic acid (MW=45,000-50,000):1.0 g

Ethyl alcohol (96°): 36.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be') q.s.p.: pH 8

This hair setting lotion when applied to bleached hair imparts thereto apearly linden coloration.

EXAMPLE 51

The following solution is prepared:

Dye of Example 17: 0.15 g

Copolymer of 90% vinyl acetate- 10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Triethanolamine, q.s.p.: pH 6.5

This hair setting lotion when applied to bleached hair imparts thereto avery luminous palm tree green coloration.

EXAMPLE 52

The following solution is prepared:

Dye of Example 3: 0.1 g

Butyl glycol: 5.0 g

Lauryl alcohol oxyethylenated with 10.5 moles of ethylene oxide: 5.0 g

Ammonia (22° Be') q.s.p.: pH 8

Water, q.s.p.: 100.0 g

This solution when applied to bleached hair for 20 minutes at 40° C.,after rinsing and drying imparted thereto a pearly light greencoloration.

EXAMPLE 53

The following solution is prepared:

Dye of Example 15: 0.2 g

Ethyl alcohol (96°): 40.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 9.5

This solution when applied to bleached hair for 20 minutes at ambienttemperature, after rinsing and shampooing imparted thereto a pearlyappearance with silvery green glints.

EXAMPLE 54

The following solution is prepared:

Dye of Example 7: 0.05 g

Copolymer of 90% vinyl acetate- 10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 9

This hair setting lotion when applied to bleached hair imparts thereto alight bronze green coloration with golden glints.

EXAMPLE 55

The following solution is prepared:

Dye of Example 3: 0.15 g

Copolymer of 90% vinyl acetate- 10% crotonic acid (MW=45,000-50,000):1.0 g

Ethyl alcohol (96°): 36.0 g

Ammonia (22° Be'), q.s.p.: pH 5.5

Water, q.s.p.: 100.0 g

This hair setting lotion when applied to bleached hair imparts thereto avervain coloration.

EXAMPLE 56

The following solution is prepared:

Dye of Example 1: 0.1 g

Copolymer of 90% vinyl acetate- 10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Triethanolamine, q.s.p.: pH 7

This hair setting lotion when applied to bleached hair imparts thereto abeige coloration with metallic glints.

EXAMPLE 57

The following solution is prepared:

Dye of Example 4: 0.05 g

Copolymer of 90% vinyl acetate- 10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Triethanolamine, q.s.p.: pH 5

This hair setting lotion when applied to bleached hair imparts thereto apearly light beige coloration with golden green glints.

EXAMPLE 58

The following solution is prepared:

Dye of Example 2: 0.1 g

Copolymer of 90% vinyl acetate- 10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Ammonia (22° Be') q.s.p.: pH 6

Water, q.s.p.: 100.0 g

This hair setting lotion when applied to bleached hair imparts thereto alinden coloration.

EXAMPLE 59

The following solution is prepared:

Dye of Example 13: 0.1 g

Ethyl alcohol (96°): 40.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 10

This solution when applied to bleached hair for 20 minutes at 40° C.after rinsing and shampooing imparted thereto a pearly appearance withgolden glints.

EXAMPLE 60

The following solution is prepared:

Dye of Example 12: 0.1 g

Copolymer of 90% vinyl acetate--10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 9

This hair setting lotion when applied to bleached hair imparts thereto agolden sand coloration.

EXAMPLE 61

The following solution is prepared:

Dye of Example 3: 0.1 g

Butylglycol: 5.00 g

Lauryl alcohol oxyethylenated with 10.5 moles of ethylene oxide: 5.00 g

N-[(4'-hydroxy)phenyl]-2,6-dimethyl benzoquinonimine: 0.20 g

N-[(4'-dimethylamino)phenyl]-benzoquinoneimine: 0.05 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 7.5

This solution when applied to bleached hair for 10 minutes at 35° C.,after rinsing and shampooing imparted thereto a steel blue graycoloration.

EXAMPLE 62

The following solution is prepared:

Dye of Example 7: 0.075 g

4-methyl-2,5-diamino phenol dihydrochloride: 0.05 g

Nitroparaphenylene diamine: 0.05 g

Ethyl alcohol (96°): 15.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 9.5

This solution when applied to 95% naturally white hair for 10 minutes at35° C., after rinsing and shampooing imparted thereto a chestnutcoloration with violet glints.

EXAMPLE 63

The following solution is prepared:

Dye of Example 9: 0.1 g

Nitroparaphenylene diamine: 0.05 g

N-[(4'-amino)phenyl]-2-methyl-5-amino benzoquinoneimine: 0.05 g

Copolymer of 90% vinyl acetate--10% crotonic acid (MW=45,000-50,000):2.00 g

Ethyl alcohol (96°): 50.00 g

Water, q.s.p.: 100.00 g

Triethanolamine, q.s.p.: pH 6

This hair setting lotion when applied to bleached hair imparts thereto arose beige coloration with golden glints.

EXAMPLE 64

The following solution is prepared:

Dye of Example 16: 0.15 g

Nitroparaphenylene diamine: 0.1 g

N-[(4'-amino)phenyl]-2-methyl-5-amino benzoquinoneimine: 0.15 g

Butyl glycol: 5.00 g

Lauryl alcohol oxyethylenated with 10.5 moles of ethylene oxide: 5.00 g

Water, q.s.p.: 100.00 g

Ammonia (22° Be') q.s.p.: pH 7.5

This solution when applied to bleached hair for 20 minutes at ambienttemperature, after rinsing and shampooing imparts thereto a goldenbronze coloration.

EXAMPLE 65

The following solution is prepared:

Dye of Example 5: 0.15 g

Acetate of toluene blue: 0.025 g

1-γ-aminopropylamino anthraquinone: 0.1 g

Copolymer of 90% vinyl acetate--10% crotonic acid (MW=45,000-50,000):1.0 g

Ethyl alcohol (96°): 36.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 7

This hair setting lotion when applied to bleached hair imparts thereto atin gray coloration.

EXAMPLE 66

The following solution is prepared:

Dye of Example 18: 0.1 g

Copolymer of 90% vinyl acetate--10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be') q.s.p.: pH 8

This hair setting lotion when applied to bleached hair imparts thereto asilvery beige coloration with green glints.

EXAMPLE 67

The following solution is prepared:

Dye of Example 19: 0.1 g

Copolymer of 90% vinyl acetate--10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Triethanolamine, q.s.p.: pH 7

This hair setting lotion when applied to bleached hair imparts thereto apearly almond green coloration.

EXAMPLE 68

The following solution is prepared:

Dye of Example 20: 0.15 g

Copolymer of vinyl acetate-crotonic acid (Example 67): 2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Triethanolamine, q.s.p.: pH 7

This hair setting lotion when applied to bleached hair imparts thereto agolden light bronze coloration.

EXAMPLE 69

The following solution is prepared:

Dye of Example 21: 0.125 g

Ethyl alcohol (96°): 40.0 g

Water, q.s.p.: 100.0 g

Lactic acid, q.s.p.: pH 5

This solution when applied to bleached hair for 20 minutes at ambienttemperature, after rinsing and shampooing, imparts thereto a metallicgreen coloration.

EXAMPLE 70

The following solution is prepared:

Dye of Example 25: 0.15 g

Copolymer of 90% vinyl acetate--10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Triethanolamine, q.s.p.: pH 7

This hair setting lotion when applied to bleached hair imparts thereto apearly light green coloration.

EXAMPLE 71

The following solution is prepared:

Dye of Example 28: 0.25 g

Copolymer of 90% vinyl acetate--10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Triethanolamine, q.s.p.: pH 7

This hair setting lotion when applied to bleached hair imparts thereto asilvery almond green coloration.

EXAMPLE 72

The following solution is prepared:

Dye of Example 27: 0.1 g

Copolymer of 90% vinyl acetate--10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Triethanolamine, q.s.p.: pH 8

This hair setting lotion when applied to bleached hair imparts thereto avervain coloration.

EXAMPLE 73

The following solution is prepared:

Dye of Example 24: 0.1 g

Copolymer of 90% vinyl acetate--10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 9

This hair setting lotion when applied to bleached hair imparts thereto alinden green coloration.

EXAMPLE 74

The following solution is prepared:

Dye of Example 22: 0.05 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 9.5

This solution when applied to 95% naturally white hair for 20 minutes atambient temperature, after rinsing and shampooing imparts thereto ametallic dark green coloration.

EXAMPLE 75

The following solution is prepared:

Dye of Example 23: 0.25 g

Copolymer of 90% vinyl acetate--10% crotonic acid (MW=45,000-50,000):2.0 g

Ethyl alcohol (96°): 50.0 g

Water, q.s.p.: 100.0 g

Triethanolamine, q.s.p.: pH 6

This hair setting lotion when applied to bleached hair imparts thereto alight bronze green coloration.

EXAMPLE 76

The following solution is prepared:

Dye of Example 26: 0.15 g

Ethyl alcohol (96°): 35.0 g

Water, q.s.p.: 100.0 g

Ammonia (22° Be'), q.s.p.: pH 10

This solution when applied to 95% naturally white hair for 20 minutes at30° C. imparts thereto, after rinsing and shampooing, a very silveryalmond green coloration.

EXAMPLE 77

The following solution is prepared:

Dye of Example 31: 0.005 g

Isopropanol: 20.0 g

Butyl monoester of the copolymer of methyl vinyl ether/maleic anhydride(sold by GAF under the trade name ES 421): 1.0 g

2-amino-2-methyl propanol, q.s.p.: pH 7

Water, q.s.p.: 100.0 g

This hair setting lotion when applied to previously bleached hair, afterdrying imparts thereto an ash blond coloration with greenish glints.

EXAMPLE 78

The following solution is prepared:

Dye of Example 29: 0.5 g

Copolymer of 70% polyvinyl pyrrolidone 30% vinylacetate (MW=40,000): 3.0g

Ethyl alcohol (96°): 70.0 g

2-amino-2-methyl propanol, q.s.p.: pH 8

Water, q.s.p.: 100.0 g

This hair setting lotion when applied to white hair imparted thereto,after drying, a bronze green coloration.

EXAMPLE 79

The following solution is prepared:

Dye of Example 30: 0.25 g

Isopropanol: 50.0 g

Copolymer of 40% polyvinyl pyrrolidone--60% vinyl acetate (MW=100.000):2.0 g

Monoethanolamine, q.s.p.: pH 9.5

Water, q.s.p.: 100.0 g

This hair setting lotion when applied to gray hair imparts thereto afterdrying a seal gray coloration.

EXAMPLE 80

The following solution is prepared:

Dye of Example 2: 0.2 g

Ethyl alcohol (96°): 60.0 g

Copolymer of 30% polyvinyl pyrrolidone 70% vinyl acetate (MW=160,000):1.0 g

Ammonia (22° Be'), q.s.p.: pH 7.5

Water, q.s.p.: 100.0 g

This hair setting lotion when applied to bleached hair imparts theretoafter drying a camomile coloration.

EXAMPLE 81

The following solution is prepared:

Dye of Example 6: 0.1 g

Isopropanol: 30.0 g

Polyvinylpyrrolidone (MW=40,000): 3.0 g

Triethanolamine, q.s.p.: pH 10

Water, q.s.p.: 100.0 g

This hair setting lotion when applied to white hair imparts theretoafter drying a linden coloration.

EXAMPLE 82

The following solution is prepared:

Dye of Example 11: 0.1 g

Ethanol (96°): 50.0 g

Terpolymer of 80% vinyl acetate, 15% allyl stearate, 5% allyloxyaceticacid viscosity (5% DMF solution-ebullition of ether)4.4-5 cps: 1.5 g

Monoethanolamine, q.s.p.: pH 6

Water, q.s.p.: 100.0 g

This hair setting lotion when applied to gray hair imparts thereto afterdrying a greenish yellow coloration.

EXAMPLE 83

The following solution is prepared:

Dye of Example 29: 0.2 g

Polyethylene glycol tertiary dodecyl thio ether: 5.0 g

Stearyl alcohol: 20.0 g

Sodium cetyl stearyl sulfate: 3.0 g

Ethyl alcohol (96°): 10.0 g

Diethanolamide of coconut and coprah: 4.0 g

Acetic acid, q.s.p.: pH 8

Water, q.s.p.: 100.0 g

This cream is applied for 15 minutes to previously bleached hair. Afterrinsing, shampooing, rinsing and drying there is imparted thereto agreenish blond coloration with golden glints.

EXAMPLE 84

The following solution is prepared:

Dye of Example 2: 0.05 g

N-[(6-hydroxy-1-oxa-4-aza-1,2,3,4-tetrahydro-7-naphthyl]-3-methoxybenzoquinone diimine: 0.05 g

Amino acetate of N-[(4'-amino-2'-methoxy-5'-methyl)vinyl]-3-amino-2-azabenzoquinone diimine: 0.05 g

4,4'-dihydroxy-2-amino azo benzene: 0.05 g

Butyl glycol: 5.0 g

Monoethanolamine, q.s.p.: pH 9.5

Water, q.s.p.: 100.0 g

This solution when applied to white hair for 25 minutes imparts thereto,after rinsing, shampooing, rinsing and drying a bottle green coloration.

The same solution when applied to gray hair imparts thereto a pine greencoloration.

What is claimed is:
 1. A quaternary ammonium salt of adiaminobenzoquinone of the formula ##STR42## wherein R₁, R₂, R₃ and R₄each independently represent a member selected from the group consistingof hydrogen, halogen, lower alkyl and lower alkoxy;R₅ represents amember selected from the group consisting of hydrogen, lower alkyl,hydroxy lower alkyl and amino alkyl of the formula ##STR43## wherein nis 2-6 and R₈ and R₉ each independently represent a member selected fromthe group consisting of hydrogen, lower alkyl and hydroxy lower alkyl;and Z is ##STR44## wherein R₆ and R₇ each independently are selectedfrom the group consisting of lower alkyl, hydroxy lower alkyl, carbamyllower alkyl, acetylamino lower alkyl, mesylamino lower alkyl,benzoylamino lower alkyl and ##STR45## wherein n is 2-6 and R₁₀ and R₁₁each independently are selected from the group consisting of loweralkyl, hydroxy lower alkyl, acetylamino lower alkyl or R₁₀ and R₁₁together with the nitrogen atom to which they are attached form aheterocycle selected from the group consisting of morpholinyl andpiperidinyl.
 2. A quaternary ammonium salt of a diaminobenzoquinone ofthe formula ##STR46## wherein R₁, R₂, R₃ and R₄ each independentlyrepresent a member selected from the group consisting of hydrogen,halogen, lower alkyl and lower alkoxy;R₅ represents a member selectedfrom the group consisting of hydrogen, lower alkyl, hydroxy lower alkyland amino alkyl of the formula ##STR47## wherein n is 2-6 and R₈ and R₉each independently represent a member selected from the group consistingof hydrogen, lower alkyl and hydroxy lower alkyl; and Z is ##STR48##wherein one of R₆ and R₇ is selected from the group consisting of loweralkyl, hydroxy lower alkyl, carbamyl lower alkyl, acetylamino loweralkyl, mesylamino lower alkyl, benzoylamino lower alkyl and the other ofsaid R₆ and R₇ is ##STR49## wherein n is 2-6 and R₁₀ and R₁₁ eachindependently are selected from the group consisting of lower alkyl,hydroxy lower alkyl, acetylamino lower alkyl or R₁₀ and R₁₁ togetherwith the nitrogen atom to which they are attached form a heterocycleselected from the group consisting of morpholinyl and piperidinyl. 3.The quaternary ammonium salt of claim 2 which is 2-amino-5-[4'-N-(ethyl,β-N-methyl piperidinium-ethyl)amino anilin]-1,4-benzoquinone iodide. 4.The quaternary ammonium salt of claim 2 which is2-N-β-hydroxyethylamino-5-[4'-[N-ethyl,β-(methylpiperidinium)ethyl]-aminoanilino]-1,4-benzoquinone iodide.
 5. A quaternary ammonium salt of adiaminobenzoquinone of the formula ##STR50## wherein R₁, R₂, R₃ and R₄each independently represent a member selected from the group consistingof hydrogen, halogen, lower alkyl and lower alkoxy,R₅ represents amember selected from the group consisting of hydrogen, lower alkyl andlower alkyl substituted by at least one of hydroxy or amino alkyl of theformula ##STR51## wherein n is 2-6 and R₈ and R₉ each independentlyrepresent a member selected from the group consisting of hydrogen, loweralkyl, hydroxy lower alkyl, acylamino lower alkyl wherein the acylmoiety has 2-5 carbon atoms or R₈ and R₉ together with the nitrogen atomto which they are attached form a heterocycle selected from piperidinyland morpholinyl; and Z is ##STR52## wherein one of R₆ and R₇ is selectedfrom the group consisting of lower alkyl, hydroxy lower alkyl, carbamyllower alkyl, acetylamino lower alkyl, mesylamino lower alkyl andbenzoylamino lower alkyl, and the other of said R₆ and R₇ is ##STR53##wherein n is 2-6 and R₁₀ and R₁₁ each independently are selected fromthe group consisting of lower alkyl, hydroxy lower alkyl, acetylaminolower alkyl or R₁₀ and R₁₁ together with the nitrogen atom to which theyare attached form a heterocycle selected from the group consisting ofmorpholinyl and piperidinyl.
 6. A quaternary ammonium salt of adiaminobenzoquinone of the formula ##STR54## wherein R₁, R₂, R₃ and R₄each independently represent a member selected from the group consistingof hydrogen, halogen, lower alkyl and lower alkoxy;R₅ represents amember selected from the group consisting of hydrogen, lower alkyl,lower alkyl substituted by at least one of hydroxy or amino alkyl of theformula ##STR55## wherein n is 2-6 and R₈ and r₉ each independentlyrepresent a member selected from the group consisting of hydrogen, loweralkyl, hydroxy lower alkyl, acylamino lower alkyl wherein the acylmoiety has 2-5 carbon atoms or together R₈ and R₉ form with the nitrogenatom to which they are attached a six-membered heterocycle selected fromthe group consisting of piperidinyl and morpholinyl; and Z is selectedfrom the group consisting of hydroxyl and ##STR56## wherein R₆ and R₇each independently are selected from the group consisting of hydrogen,lower alkyl, hydroxy lower alkyl, carbamyl lower alkyl, acylamino loweralkyl wherein the acyl moiety has 2-5 carbon atoms, mesylamino loweralkyl, benzoylamino lower alkyl and ##STR57## wherein n is 2-6 and R₁₀and R₁₁ each independently are selected from the group consisting oflower alkyl, lower alkyl substituted by at least one of hydroxy oracylamino, or R₁₀ and R₁₁ together form with the nitrogen atom to whichthey are attached a six-membered heterocycle selected from the groupconsisting of piperidinyl and morpolinyl,with the proviso that at leastone of R₅ and Z contains a tertiary amino group.
 7. A quaternaryammonium salt of a diaminobenzoquinone of the formula ##STR58## whereinR₁, R₂, R₃ and R₄ each independently represent a member selected fromthe group consisting of hydrogen, halogen, lower alkyl and loweralkoxy;R₅ represents ##STR59## wherein n is 2-6 and R₈ and R₉ eachindependently represent a member selected from the group consisting oflower alkyl and hydroxy lower alkyl; and Z is selected from the groupconsisting of hydroxyl and ##STR60## wherein R₆ and R₇ eachindependently are selected from the group consisting of hydrogen, loweralkyl, hydroxy lower alkyl, carbamyl lower alkyl, acylamino lower alkylwherein the acyl moiety has 2-5 carbon atoms, mesylamino lower alkyl,benzoylamino lower alkyl and ##STR61## wherein n is 2-6 and R₁₀ and R₁₁each independently are selected from the group consisting of loweralkyl, lower alkyl substituted by at least one of hydroxy or acylamino,or R₁₀ and R₁₁ together form with the nitrogen atom to which they areattached a six-membered heterocycle selected from the group consistingof piperidinyl and morpholinyl.
 8. A quaternary ammonium salt of adiaminobenzoquinone of the formula ##STR62## wherein R₁, R₂, R₃ and R₄each independently represent a member selected from the group consistingof hydrogen, halogen, lower alkyl and lower alkoxy;R₅ represents amember selected from the group consisting of hydrogen, lower alkyl,hydroxy lower alkyl and amino alkyl of the formula ##STR63## wherein nis 2-6 and R₈ and R₉ each independently represent a member selected fromthe group consisting of hydrogen, lower alkyl and hydroxy lower alkyl;and ##STR64## wherein R₆ and R₇ each independently are selected from thegroup consisting of lower alkyl, hydroxy lower alkyl, carbamyl loweralkyl, acetylamino lower alkyl, mesylamino lower alkyl, benzoylaminolower alkyl, and ##STR65## wherein n is 2-6 and R₁₀ and R₁₁ eachindependently are selected from the group consisting of lower alkyl,hydroxy lower alkyl, acetylamino lower alkyl or R₁₀ and R₁₁ togetherwith the nitrogen atom to which they are attached form a heterocycleselected from the group consisting of morpholinyl and piperidinyl. 9.The quaternary ammonium salt of 2-N-β-hydroxyethylamino-5-[4'-morpholinoanilino]-1,4-benzoquinone.